Textile treatment with novel aqueous dispersion to achieve water-repellent finishes



United States Patent Ofiice 2,971,930 Patented Feb. 14, 1961 No Drawing.Filed May 22, 1956, Ser. No. 586,357 '10 Claims. (Cl. 260-21) Thepresent invention relates to aqueous dispersions of water-repellentagents, their application to textile materials and the resultingwater-repellent textile materials.

An object of the invention is to provide improved compositions forimparting water-repellent efiects.

Another object of the invention is to provide an improved durablewater-repellent agent for textile materials.

A further object of the invention is to provide an improved method forimparting to textile materials a waterrepellent finish which is durableto laundering and dry cleaning.

Still another object of the invention is to provide an improved textilematerial having a water-repellent finish which is durable to launderingand dry cleaning.

Other objects and advantages of the invention will be apparent to thoseskilled in the art, especially upon consideration 'of the detaileddisclosure hereinbelow.

The present invention concerns an aqueous dispersion of anaminotriazine-aldehyde resinous condensate; a waxlike compound with amelting point above about 100 F. and containing a hydroxylated aliphaticacyl chain of at least 12 carbon atoms; a hydrophilic protectivecolloid; and one or more emulsifiers of the group consisting ofsulfonated and sulfated fatty acids, alcohols and esters with analiphatic chain of at least 8 carbon atoms, sulfona-ted lignin,condensation products of polyalkylene polyamines with fatty acidscontaining 8 carbon atoms, dialkyl alkylol alkylam-ides quaternaryammonium salts and water-dispersible reaction products of an aliphaticamine containing at least 12 carbon atoms with epichlorohydrin. Inaddition, it relates to the treatment of textile materials with thesenovel dispersions and the product of such treatment. Optionally, thecompositions may contain a hydrocarbon or ester Wax melting about 100unalkylated and alkylated aminotriazine-aldehydecom densates and theirpreparation is disclosed in Widmer et al. Patents Nos. 2,197,357 and2,191,362; and hence need not be repeated here. The triaminoanddiaminotn'azines are preferred, especially melamine and the guanaminessuch as acetoguanamine and propioguanamine. Of these, the methyl ethersof methylol melamines provide the optimum results, and these may containfrom 1 to 6 mols of combined formaldehyde and 1 to 6 mols of combinedmethanol per mol of melamine. The combined methanol content does, ofcourse, not exceed the combined formaldehyde content on a molar basis.For

colloidal solution exhibiting 2 each 100 parts total of the waxymaterials described hereinafter, between about 30 and about 600 parts ofthe aminotriazine resin may be employed and the preferred amount isbetween about 60 and about 300 parts. The

aminotriazine-aldehyde condensate may be employed either in essentiallymonomeric form or in the partially polymerized colloidal state in acidsolution as described in Patents Nos. 2,345,543 and 2,609,307. Textilefinishing resins of the urea-formaldehyde and substitutedureaformaldehyde type may not be substituted for the amino.-

. triazine resins in the novel compositions because the finish impartedthereby to textiles has no permanence or durability whatsoever to drycleaning and laundering.

. methylene urea, and their methyl ethers.

Optionally, an additional textile finishing agent derived from urea maybe employed along with the aminotriazine resin for the purpose ofreducing the yellowing which occurs to some extent due to the retentionof chlorine by a melamine resin finish on a textile fabric. This isaccomplished without any improvement or decrease in the durability orspray rating of textile fabrics finished ac cording to the presentinvention. Among the suitable agents for decreasing yellowing areessentially monomeric methylated methylol ureas and their water-solublelower polymers, and the unalkylated and alkylated formaldehydecondensates of alkylene ure'as like dimethylol ethylene urea, dimethylolpropylene urea, dimethylol tri- These substances and their preparationare well understood and they may contain from 1 to 4 mols of combinedformal- F. in a quantity ranging up to about 4 times the weight of saidhydroxylated a hydroxylated saturated dehyde per mol of urea or ureaderivative as well as a combined methanol content ranging from about 20%up to but not exceeding the formaldehyde content on a molar basis. The.water-soluble lower polymers of methylated methylol urea may be easilyobtained by refluxing with heating about 2.5 mols of 'paraformaldehydeper mol of urea in 21 methanol medium for several hours at an alkalinepH, cooling, adding methanol in stoichiometric excess, adjusting themixture to a moderately acid pH, refluxing for a short period, thenstopping the reaction by cooling and adjusting the pH to a moderatelyalkaline value. These substances may be employed in quantities rangingup to but not exceeding the weight of aminotriazine resin, and it isgenerally recommended that at least about 6.6 and preferably about 30 tobe used, based on the weight ofaminotriazine resin, when. chlorineretention is a significant problem. For producing a waterrepellenteffect on porous materials like cloth, leather, etc., it is seldomdesirable to have more than a total of 600 parts of urea derivative andaminotriazine-aldehyde condensate in a dispersion containing 100 partsof waxy material or materials.

The hydrophobic component of the novel oil-in-water dispersi ns is, ofcourse, in the dispersed phase. This Water-insoluble wax-like materialcontains a compound with a melting point above 100 F. and preferablyabove P. which has a hydroxylated saturated fatty acyl radical of atleast 12 carbon atoms and preferably between 16 and 30 carbon atoms. Inthese substances, one or more hydroxy groups are attached to one or morecarbon atoms in the alkyl chain other than the acyl "or carboxyliccarbon atoms. Thus this component may be higher fatty acid or an esterthereof with a monohydric or polyhydric alcohol including glycerol.Among the suitable compounds are hydrogenated castor oil which appearsto produce the optimum results, hydrogenated ricinoleic monoandd-i-glycerides, 9,10-dihydroxystearic acid, methyl, bu-tyl, cetyl andother alkyl esters of hydrogenated ricinoleic acid, lauryl-9,l0-dihydroxy stearate, and mixtures thereof.

A certain percentage of a hydrocarbon or an ester wax melting aboveabout 100 F. may be blended with the hydroxylated waxy material withexcellent results. In

amass this'hydrocarbon category are included various grades of paraflin,ozokerite, scale wax, micro-crystalline waxes, and so forth. A fewexamples of suitable ester Waxes ofnatui'al or synthetic origin arecarnauba, japan, montanycandelilla, beeswax and other insect waxes.Refined paraffin wax is preferred when the dispersion is intended forthe treatment of light colored textiles and grades melting above about120 F. are recommended 'for'best results. Mineral waxes are cheaperthan'hydroxylated fatty acyl'compounds; hence, 'a blend-of the two'ieduc'es the cost of the textiletreatment. In'addition, it has beenfound that withinproper limitsfa hydrocarbon wax actually enhances thewater-repellent characteristicsof the textile finish and somewhatimproves its durability to dry cleaning and laundering. Blends of equal'parts of v the two waxy materials seem to appear to be the optimumHowever, the hydrocarbon or ester wax may de- Tsirably constitute fromabout up to about 80% of the weight of the hydrophobiccomponent; beyondthat, the dry cleaning durability of the textile finish suffers.

The treating agent also contains a small quantity of a hydrophilicprotective colloid which serves to stabilize the suspension ordispersion. Polyvinyl alcohol appears to provide the best results andthe lower viscosity grades are especially recommended; however, avariety of other materials can be used including lower viscosity gradesof carboxymethyl cellulose, gum ghatti, gum arabic, gelatin,polyacrylamide, polymethylolacrylamide, polymethacrylamide,polymethylolmethacrylamide, and the like. In general, any hydrophilicprotective colloid that is free of rewetting tendencies after drying issuitable in the present invention. Based on the total weight of waxyingredients, the protective colloids are desirably present in quantitiesl'ranging from about 0.5 to about 20% or more on a dry basis.v IA higherfatty alcohol containing from about 12 up to .30 or more carbon atoms isan optional but often highly desirable component of the mixture,especially where a hydrocarbon wax is present. This alcohol is thoughtto act as a coupling agent which improves the miscibility of thehydroxylated waxy material and the mineral wax. More. importantly, it isa stabilizer which provides long shelf life for the wax dispersion. Thisobviates any necessity for preparing the wax dispersion at the place itis to be used, a feature which is often important inase much as textilefinishing plants, etc. are seldom equipped with good emulsificationequipment such as homogenize rs. Thus it is possible to sell theingredients for preparing the novel dispersions as two items having aprolonged storage life, namely an aqueous solution of the aminotriazineresin and an aqueous dispersion of the waxy material. In addition, itappears that the fatty alcohol facilitates the preparation of waxdispersions on a large scale and it is well known that large quantitiesof wax emulsions are often less stable than smaller laboratory batches.Cetyl alcohol is preferred for the purpose but one or more othersaturated and unsaturated fatty alco- V hols may be employed, includinglauryl, myristyl, stearyl, palrnitoyeyl, oleyl, cetoleyl alcohols andthe like may be substituted, if desired. The recommended quantities arefrom about 1 to 6 parts for each 100 parts of total waxy components.

Many emulsifiers or dispersing agents are unsuitable for the presentcompositions by reasonof incompatibility,.a tendency toward rewettingafter drying, etc. However, certain classes of Wetting or dispersingagents have been discovered which produce good results. trnong these aresulfonated or sulfated higher fatty acids,alcohols and esters containingan aliphatic chain of at' least 8 but seldom over about 30 carbon atoms.Sulfated fatty alcohols are preferred for the purpose and thisexpression is used herein to include the alkaline metal salts of suchmaterials since this is the form in which T Ii Y @FQQQ FLQQR fi fii ll 1t m th man suitable materials encompass esters which term is usedhalogen at'om lbs. per square inch.

herein to include the esters of polyhydric alcohols such as ethyleneglycol, glycerine, etc. as well as monohydric alcohols. Moreover, thealiphatic chains of these materials may be either saturated orunsaturated prior to the sulfonation or sulfation treatment. Among themany suitable materials are 'caprylyl, capryl, lauryl, myristyl,

'ce'tylfand ste'arylalc'ohol sulfates, sulfonated ricinoleyl alcohol,etc., "and "their alkali salts; methyl, 'butyl and other alkyl esters ofthe aforementioned alcohols; sulfated caprylic, lauric, palmiticstearic, oleic, linoleic, linolenic acids as well as sulfonat'edricinoleic acid andthe 'fatty acid (S te 30 carbon atoms) such ascapric, lauric,

and stearic acids, fre'quently accompanied by a lower 'aliphaticacidsuch as formic orpropionic'acid in minor proportion; 'dialkyl' alk'ylolalkylamide quaternary ammoniurn salts as exemplified by palmitamidoethyldiethyl gamm'a hydroxypropyI ammonium chloride, and similar compounds"containing two'loweralkyl groups of about 1 to 4 carbon atoms, a 1 to 4carbon alkylol radical, a

and a radi'cal containing a higher alkylamide of about 8' i030carbonscombined with a 1 to 4 carbon alkyh'g'roup; and thewater-dispersible reaction products-of long chain aliphatic aminescontaining from Sto about 22 carbon atoms, like dodecylamine andeicosylamine, with epichlorohydrin can be employed for the purpose.Suitable amine-epichlorohydrin reaction Qp'roduc'ts and theirpreparation are disclosed in detail in Lundberg application Serial No.393,246, filed November 19, 1953 (Patent No. 2,753,372) and these may beneutralized with acetic or another lower carboxylic acid ratios mayrange from about 1:2 to 2:1 and this particular group of compounds ispreferred for use under acid for greater stability. Theamine-epichlorohydrin molar conditions, as for instance, where theresinous component is in the acid colloid form. Based on the totalweight of waxy materials, the dispersing agents described may be presentin amounts ranging from about 0.5 to 15%, and for most purposes, betweenabout 1 and about 4% is recommended. Too much may cause unwantedrewetting.

In preparing the novel dispersions the hydroxylated waxy material may bemelted and thoroughly blended with any hydrocarbon wax or fatty alcoholwhich may be added at a temperature of 235 F. for example. Meanwhile,the protective colloid may be stirred into about partsby weight of waterwith heating until it is dissolved; then the dispersing agent may beadded and the aqueous phase heated to about l80-l95 F. Next, about 30parts of the molten waxy mixture may be combined with the aqueous phasewith vigorous agitation followed by passing the crude emulsion through ahomogenizer at 3000 u 7 After this, the suspension of waxlike materialis cooled rapidly to 'a temperature below The novelcompositions may beused in a variety of applications in the textile, paper and leatherfields. They are especially intended for the water proofing of porousmaterials' by impregnating the materials with the aqueous dispersionfollowedby drying andcuring to convert the iaminotriazine-aldehydecondensate to the substantially water-insoluble state. This curing isaccomplished at elevated temper atures of preferably about 200 to 325driven higher if smoking due 'to vaporizing a portion aqueous waxdispersions is of the waxy matter from the impregnated material duringcuring is not objectionable. In compositions containing a colloidal orpartially polymerized aminotriazine resin, heating is not required tocure the resin but is usually preferred in commercial operations inorder to expedite of acrylonitrile with vinyl acetate, methyl acrylate,the .vinyl pyridines, etc., polyethylene glycol terephthalate and caseinfibers. The dispersions may be applied to either fibers or fabrics byany suitable means such as padding, spraying, immersion, roll coating,etc. The treatment of most fabrics is well exemplified by passing a thefabric through a dispersion containing from about 2 to about 35% solidsand preferably about to about 20% solids with the squeeze rolls adjustedto. provide a dry pick up between about 1 and about 35 and preferablybetween about 5. and about 20% based on the weight'of dry fabric. Thewet impregnated fabric is then dried and cured, usually but notnecessarily in a single operation by heating at between about 200 andabout 325 F. for a period between about and about 4 minutes. Wherenecessary or desirable the curing is catalyzed by the presence of asuitable catalyst known in the art such as magnesium chloride, aminehydrochlorides, diammonium phosphate and other acidic or latent acidaccelerators.

The function of the various components in the new composition is notfully understood. There is some reason to believe that duringcuring, anoncarboxylic hydroxyl group on the hydroxylated wax-like substancereacts with a methoxymethyl or methylol radical in the aminotriazinecompound with a splitting off of water or methanol in what isessentially a transesterification reaction. While this theory wouldappear to be confirmed by the outstanding durability of textile finishesimparted with the present invention, this merely is offered as apossible explanation; and the invention is not limited to this theorysince it has not been established with certainty.

For a better understanding of the nature and objects of this invention,reference. should be had to the following illustrative examples in whichall proportions are stated in terms of weight unless otherwise indicatedtherein. In addition, all testing of fabrics is carried out by standardmethods adopted by the American Association of Textile Chemists andColorists (AATCC) unless otherwise stated.

Following the procedure outlined above, a series of prepared from thefollowing constituents.

cured for three minutes at 300 TABLE I Wax Dispersions A B 0 D E F Slackwa 14. o

Refined paratfin wax (133- F., .P.) 14. 10 14. 0 9. 3 18. 7 14. 0Hydrogenated casto 14. 10 14. 0 18. 7 9. 3 14.0 14. 0 Polyvinylalcohol 1. 25 0. 3 0. 3 0. 3 3. 0 0. 3 Sodium lauryl sulfate 0. 50 0. 50. 5 0. 5 0. 5 0. 5 Cetyl al 0. 90 Water 69. 15 71. 2 71. 2 71. 2 68. 571. 2

These are finely divided suspensions of the waxy materials in waterwhichare stable indefinitely. In the textilefinishing operations describedhereinbelow,-they are employed in more dilute form in combination with aresinous material of the type described herein. Suitable pad baths aredesirably prepared by warming the wax A pad bath is made up containing6.25% of solids from wax dispersion A and 6.25% by weight of methylatedtrimethylol melamine (67% methylated) prepared similarly. to Example 2in British Patent 566,347 along with a magnesium chloride solutionequivalent to 0.75% anhydrous MgCl Rayon challis, x 80 cotton percaleand a 5.5 ounce cotton poplin fabrics are successively padded throughthis solution using 1 dip and l nip to give wet pickups of 93%, 76% and72%, respectively. All of the fabrics are dried at 225 F. and the rayonis F. while the cotton fabrics are cured in a similar oven at 350 F. for1.5 minutes.

Other samples of the same three fabrics are treated in the same mannerusing a bath containing the same quantity of resin and catalyst but noneof wax dispersion A.

The two cotton poplins are subjected to Stoll flex abrasion tests onlyand it is found that the sample treated with the resin solution alonestands 99 cycles whereas the material treated with both resin and waxymaterials has a rating of 204 cycle. I

The rayon challis and 80 x 80 cotton fabrics are tested for wrinklerecovery, tensile and tear strength and waterrepellent characteristicsalong with untreated control samples of the same materials and thefollowing test data are obtained. During a similar trial using waxdispersion A and a larger proportion of ureaforrnaldehyde resin on rayonchallis, it is found that the treated fabric has excellent wrinkleresistance but the initial spray rating is 0.

TABLE II All cotton washes specified herein are conducted at Exliinple19 160 F. for one hour using a solution of 0.1% soap and Wt. percent0.1% sodium carbonate followed by rinsing at 160 F. -Colloi'dalinetliylated tniniethylol melamine" (resin A and all rayon launderingsare carried out at 100" F. for slids) w r 1 5.00 1 hourusing a solutionof 0.1% soap followed by rinsing 5 '-Hydr'ogenatedcitastor oil .250 at100 F. Carnauba wax 1 a r 5 2.50

7 Except where otherwise specifiedherein, all dry cleaning operationsare for a period of'one hour using a Cetyl-alcohol I I 0.14 hydrocarboncleaning solvent knowrras Varsol II. V 'Reaction;product" of 1 moloctadecylamine'with 2 a -10 mols of epichlorohydrin'with 75% of theamino :Exam groups neutralized with acetic acid 019 p .w H .3945

A treating bath ismradeu'p with equal weights of dimethylol melamine andthe solids of wax dispersion A 7 plus 8.44% mixed isopropanolaminehydrochlorides based on the weight of "the melamine compound. The -samecotton poplin is argued through this bath to a'10% by weight dry pickupfollowed bydrying and curing for 6 minutes at 290 F. The initial sprayrating of the treated fabric is 90+ and the alue after'one hour oflaundering is 70 but'the' finishis not durable to dry cleaning.

Example 3 The same cotton poplin is treated with a bath'containing equalweights of trimethylol beta-cya'nopropioguanamine and the solids of waxdispersion A along with 3.5% based on the weight of theguanamine-formaldehyde compound of an accelerator comprising essentiallydiammonium hydrogen phosphate. The'drying, curing and test procedures ofExample 2 are followed and the :finished fabric is found to have sprayratings initially of 80+ and of 70 after one hour of washing. Thisfinish also is not durable to dry cleaning.

35 ylated The partially polymerized colloidal melamine resin above isintroduced as 'a 10% aqueous. solution exhibit ing thecharacteristicblue Tyndall haze' of cationicwaterdispersible melamineresin particles aged in ac'eticacid as described in Patent No.2,609.307. An all wool flannel fabric and an'80 x"80 cotton percale'arepassed through a pad bath of the composition listed above containing nocatalyst with the squeeze rolls adiusted for a wetpick up of 100%. Afterdryingat 225 F. -for.15' minutes, it .is

found that both fabrics exhibit greatly. reduced shrinkage uponlaundering in comparison w'thuntreated samples of the same material. Inaddition, both'fabrics have excellent spray ratings which are durableto-dry cleaning and to repeated washings.

Example 20 H w Wt. percent Methylated pentamethylol melaminemeth- 7Hydrogenated castor oil 2.50 18 Candelilla wax 2.50 mm? es Polyvinylalcohol 0.22 Cetyl alcohol 0.16 Several fabrics are padded through thevarious treating baths listed in Table IH below. The resin employed 40$3222? lauryl s f elusive," ethylene dichloride is employed in lieu ofVarsol II as the dry cleaning agent.

Viscose, silk, and 80 x 80 cotton perc'alefabrics are 45 passed througha pad bath of 'the above composition to which 1.2% magnesium chloride(anhydrous basis) has been added as a catalyst with the squeezerollset-for' 85% expression. The fabrics are dried and cured in an ovenfor 6 minutes at 320 F. The resulting finish is found to impart a highdegree ofdurable water repellence coupled with good reslstance-toshrinkage, wrinkling and tearing.

TABLE III Bath Content AATCO Spray Ratings Example Wax Fabric AfterWashing After Dis- Resin Waxy Initial Dry persion Solids Solids Clean- 1hour 3 hours ing J B I 1o a 100 so 38 '10. 10 90+ 80 O 10 10 90+ .3 i8 290+ 0 F 7. 5 3. F i 5 I 2.5 70- 70 1o 5 H so+- '70 F 10 5 v 100 90 70- E7. 5 5 Spun rayon. 90+ 90+ v E 10 5 90+ so 1+ 7. 5 5 so so 70- I F 10 a100 100 so 9 Example 21 Wt. percent Methylated pentamethylolmelamine-50% methylated 4.20

. Partially polymerized methylated dimethylol urea 80% methylated 2.10Hydrogenated castor oil 3.15 Refined paraffin wax 3.15 Polyvinyl alcohol0.28 Cetyl alcohol 0.20 Sulfonated castor oil 0.11 Water 86.81

With 3.5% (based on the total Weight of resin solids) I of a catalystcomprising essentially diammonium hydrogen phosphate added to the bath,5.5 ounces cotton poplin is impregnated to pick up 10% solids based onthe dry fabric weight. After drying and curing at 290 F. for 6 minutesin an oven, the initial spray rating of the cloth is 90+. Samplessubjected to one hour of washing are found to have a spray rating of 80and other samples exposed to one hour of dry cleaning are rated at 70 inthe same test.

Fabrics woven from nylon, polyethylene glycol terephthalate, and anacrylonitrile copolymer (85% acrylonitrile, 7.5% vinyl acetate, 7.5Z-methyl -vinyl pyridine) fibers, respectively, are padded through atreating bath containing the constituents listed according to theprocedure of Example 21. All three fabrics are found to have excellentspray ratings of a substantially permanent nature, and the finishes donot exhibit detrimental effects upon exposure to chlorine bleaching.

Example 23 Methylated trimethylol melamine 6.00 Methylated dimethyloltrimethylene urea 3.00 Hydrogenated castor oil 5.00 Polyacrylamide 0.22.Sodium ligninsulfonate 0.16 vWater 85.62

A olyacrylamide with a viscosity of 10,160 centipoises (Brookfield) atconcentration in water in employed as the protective colloid in thisdispersion. Viscose rayon gabardineand 80 x 80 cotton percale areimpregnated in this bath and cured using the procedure and obtaining thesame qualifies as in Example 21.

Example 22 is repeated using the bath listed to produce fabricsexhibiting the same characteristics including a low degree of chlorineretention upon exposure to bleaches.

10 Example 25 Methylated pentamethylol melamine50% methylated 10.00Hydrogenated castor oil 2.50 Beeswax 2.50 Polyvinyl alcohol 0.22 Cetylalcohol 0.16 Stearamidopropyl dimethyl beta-hydroxyethyl ammoniumchloride 0.09 Water 84.53

An x 80 cotton fabric is impregnated with the above dispersion followingthe procedure of Example 22. Again a durable finish with high sprayrating is obtained along with good wrinkle resistance and shrinkresistance.

Example 26 Dimethylol melamine 10.00 Hydrogenated castor oil 2.50Refined parafiin wax 2.50 Polyvinyl alcohol 0.23 Reaction product of 2.9mols of. technical stearic acid per mol of tetraethylenepentamine plusv1.5% acetic acid 0.56 Water 84.21

,Cotton and viscose rayon fabrics are treated with the above dispersionin accordance with the procedure of Example 21. A wash-durablewrinkle-resistant and waterrepellent finish is obtained on both fabrics.

Example 27 Methylated trimethylol melamine 5.00 9,10-dihydroxy stearicacid 2.50 Refined parafiin wax 2.50 Polyvinyl alcohol 0.22 Cetyl alcohol0.16 Sodium lauryl sulfate 0.09 Water 89.53

A viscose rayon gabardine, and a cotton percale fabric are passedthrough the above pad bath and processed in the manner set forth inExample 21. The durable finish on both fabrics is highly water repellentand has good resistance to wrinkling and shrinkage.

Cotton poplin and cellulose acetate fabrics are finished with this bathaccording to the procedure of Example 21. The resulting finish has ahigh degree of durable water repellency coupled with good resistance toshrinkage, wrinkling and tearing.

From the above results, it is apparent that many beneficial advantagesare secured by the present invention and a number of unexpected resultsare encountered. A high degree of water repellency is obtained alongwith an excellent durability of the finish to washing whenaminotriazine-aldehyde resins are used in the combination. In addition,good durability of the water-repellent finish to dry cleaning isobtained when an alkylated aminotriazine resin is selected. On the otherhand, similar benefits are not obtainable with unreaformaldehyde resinsin combination with the same waxy materials fornot even initial waterrepellency is developed by the treatment. Dimethylol ethylene urea as asubstitute can produce a good initial spray rating on the fabric but thefinish is compositions.

not durable to either washingor dry cleaning. The presentcompositions.also producegood wrinkle resistance and shrink resistance. On rayon animportant advantage is'gained in the greatly increased .tear strength,for example more than 50% over the untreated fabric, along with asubstantial though smaller increase in tensile strength.

In comparing the effects of the novel mixtures with those obtained bythe same resins alone in the absence of the hydrophobic components, onepmticularly strange effect is noted in that addition of the waxycomponent produces 'no softening efiect. Themost important benefitsrealized over the straightresin treatments are the great improvement intear strengths ranging from about 50% on'cotton' to almost 300% on rayonin addition to the water-repellent characteristics and a doubling of theresistance to wear as measured by Stolls flex abrasion test.

The present invention possesses a significant economic advantage over awell known commercial water repellent containing melamine resinaccording .to Patent No. 2,357,273, especially when a hydrocarbon waxlike paraffin is present'in a sizable amount. "Difficulties havefrequently been encountef'dtr'om the formation of a large quantity ofa'ralther'dry foam in paid baths 'of the prior art water repellentwhereas only a-small volume of wet foam is formed on treating baths ofthenovel Although seldom necessary, the-useof suitable defoaming agentsis also contemplated herein, and it is well known that these materialsare more effective on wet foams than those of a drier nature. Thefinishes imparted-to textiles aresubstantially equal in water repellency-and-durability to washing to those obtained' withtheaforesaidcommercial product,- and' the abrasion resistance "of the"cloth is greatly improved. Also, thenew compositionscan-be catalyzedwithmagnesiurn chloride which is currently the best accelerator foraminotriazine'resins in solution; while theprior art water repellent wasincompatible with that catalyst.

While there are disclosed herein only a limited number of embodiments ofthe composition, process and product of the invention, it is possible toproduce still other embodiments without departing from the inventiveconcept set forth, and it is desired, therefore, that only suchlimitations be imposed upon the appended claims as are stated therein orrequired by the prior art.

I claim:

1. A composition of v.matter which comprises an aqueousdispersionoftl)between about 30 and about 600 parts of. a resinous component selectedfrom the group consisting of water-soluble aminotriazine-ald'ehyde resinand aqueous colloidal aminotriazinealdehyde resins and mixtures of saidaminotriazine-aldehyde resins with a water-soluble textile finishingagent selected from the group consisting of methylated methylol ureas,methylol alkylene urea and methylated methylol alkylene urea, saidmixtures containing between about 6.6 and about 100% of said textilefinishing agent based on the weight of aminotriazine-aldehyderesin; (2)100 parts of an hydrophobic component selected trom the group consist-.

ing of a wax-likev compound melting above 100 F. containing anhydroxyl-ate'd. aliphatic acyl radical of between 12 and about 30 carbonatoms and a composition comprising such a wax-like compound and a waxmelting above about Wax ilLSllchl mp iti n n Blr'ial according to claim6 and. acuring catalyst and heatbeing present in an amountexceeding'about four times the weight of said wax-like compound; ,(3)'between about 0.5' and about 20 parts of a.hydro'philic protectivecolloidfree from rewetting tendencies after'drying and (4) between about0.5 and about parts of an emulsifying agent of the groupconsistingof'sulfonated and sulfated acids, alcohols andesterscontaining an aliphatic chain of between 8 and about 30. carbon atoms,sulfonat'ed ligm'n; condensation products: of polyalkylene polyamineswithfatty acids containing between 8..and about '30 carbon atoms,dialkyl alkylol alkylamide quaternary ammonium salts andwater-dispersible reaction products .of an aliphatic arnine containingfrom 8 to about 22 carbon atoms withepichlorohydrin.

5 2. A composition according vto .claim 1 containing from betweenabout 1and about 6 parts. of an alipha'tic alcohol having between 12 and 30carbon atoms.

:3. A composition according to claim 1 in which said resinous componentis a methylated methylol melamine. 4. A composition of matter whichcomprises a stable aqueous dispersion of (l) betweenabout 30 and about600 parts byweight ofmethylated methylolmelamine selected from the groupconsisting of .water-soluble methylated methylol melamine and colloidalmethylated 15 methylol melamine; (2) 100 parts of a wax-like substanceeomprising paraffin wax melting'above 100 F. and hydrogenated castor oilmelting above 100" F. in a weight ratio not exceeding 4:1, parafiin waxto hydrogenated castor oil respectively; (3) betweenabout 0.5 and about20 parts of a hydrophilic protective colloid free from rewettingtendencies after drying; (4) between about 1 and about 6 parts of analiphatic alcohol containing between 12 and 30 carbon atoms and (5)between about 1 and about 4 parts of asulfated fattyalcohol containingbetween about 8 and about carbon atoms.

5. A composition of matter which comprises an aqueous'dispersion-of (1)between about '30 and about -600 parts ofa methylated methylol melamineselected 30 "from-the-group consisting of water-soluble methylatedmethylolinelamines and colloidal methylated methylol melamine; (2) 100parts of hydrogenated castor oil melting abovel00 F.;. (3) betweenabout..0.5 and vabout 2Q parts.,of-polyvinyl .alcoholand (4)betweenabout 0.5

735 and about 15 parts of a sulfated fatty alcohol containing between 8andabout 30 carbon atoms.

6.. Ascomposition of matter which comprises a stable aqueous. dispersionof (1) between about '32 and about .600 parts by weightof a mixturecomprising a minor 40 portion of a. substance selected from. thegroupconsisting of water-soluble methylated methylol urea, methylolalkylene ureas and methylated methylolalkylene ureas, together with amajor portion amounting toat least 30 parts of. a methylated methylolmelamine selected from the group consisting of water-soluble methylatedmethylol melamine and colloidal methylated methylol melamine; (2) 100parts of a waxy substance comprising parafin wax having at-meltingpointabove 100 and hydrogenated. castor oil having a melting point abovel00 F. in a weight ratio not exceeding about 4:1 paraflin wax tohydrogenated castor oil respectively; (3) between about 0.5 and about 20parts of an hydrophilic protective colloid free from rewett'ingtendencies after drying; (4)' between about 1 and about '6 parts ofanaliphatic alcohol containing between 12and about 30 carbon atoms; (5)and between 1 and about 4 parts of, a sulfatedv fatty alcohol containingbetween about 8 and about 30 carbon atoms.

7. A process which comprises treating textile material with acomposition according to claim 1 and a curing catalyst and heating thetreated material whereby a'durable water-repellent finish is imparted tothe textile material.

8. A process which comprises treating a textile mateing the treatedmaterial whereby a durable waterrepellent finish is imparted to thetextile material.

9. An article which comprises a; textile material having as-adurable'water-repellent-finish: the heat cured 7t! reaction-product of'acomposition according to claim =1.

(References on following page) References Cited in the file of thispatent UNITED STATES PATENTS 2,537,667 Harris Jan. 9, 19s=1 2,835,639Widmer et a1 May 20, 1958 OTHER REFERENCES 9 0 wfdmer et a1 Feb 20 4 5Bennett: commerclal Waxes, pp. 91, 113, Chem. Pub. W1dmer et a1. Apr.16, 1940 c B kl NY 1944 Au 29 1944 0., rec yn,

f Swern et 211.: J. Am. Chem. Soc. 67, 902-3 1945 Gm SePt- 1947 Speel:Textile Chemicals and Auxiliaries, pp. 206, 207, Fordemwalt 2, 1951213,299316,366-9 1952 UNITED STATES PATENT OFFICE CERTIFICATION OFCORRECTION Patent No. 2,971,930 February 14, 1961 Nathaniel J. Glade Itis hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 6, Table I, first column thereof, line 1, for "Slack was" readSlack wax columns 7 and 8, Table III, last column thereof, oppositeExample 12, for "70" read O Signed and sealed this lst day of August1961.,

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents

1. A COMPOSITION OF MATTER WHICH COMPRISES AN AQUEOUS DISPERSION OF (1)BETWEEN ABOUT 30 AND ABOUT 600 PARTS OF A RESINOUS COMPONENT SELECTEDFROM THE GROUP CONSISTING OF WATER-SOLUBLE AMINOTRIAZINE-ALDEHYDE RESINAND AQUEOUS COLLOIDAL AMINOTRIAZINE-ALDEHYDE RESINS AND MIXTURES OF SAIDAMINOTRIAZINE-ALDEHYDE RESINS WITH A WATER-SOLUBLE TEXTILE FINISHINGAGENT SELECTED FROM THE GROUP CONSISTING OF METHYLATED METHYLOL UREAS,METHYLOL ALKYLENE UREA AND METHYLATED METHYLOL ALKYLENE UREA, SAIDMIXTURES CONTAINING BETWEEN ABOUT 6.6 AND ABOUT 100% OF SAID TEXTILEFINISHING AGENT BASED ON THE WEIGHT OF AMINOTRIAZINE-ALDEHYDE RESIN, (2)100 PARTS OF AN HYDROPHOBIC COMPONENT SELECTED FROM THE GROUP CONSISTINGOF A WAX-LIKE COMPOUND MELTING ABOVE 100*F. CONTAINING AN HYDROXYLATEDALIPHATIC ACYL RADICAL OF BETWEEN 12 AND ABOUT 30 CARBON ATOMS AND ACOMPOSITION COMPRISING SUCH A WAX-LIKE COMPOUND AND A WAX MELTING ABOVEABOUT 100*F., SAID WAX IN SUCH COMPOSITIONS NOT BEING PRESENT IN ANAMOUNT EXCEEDING ABOUT FOUR TIMES THE WEIGHT OF SAID WAX-LIKE COMPOUND,(3) BETWEEN ABOUT 0.5 AND ABOUT 20 PARTS OF A HYDROPHILIC PROTECTIVECOLLOID FREE FROM REWETTING TENDENCIES AFTER DRYING AND (4) BETWEENABOUT 0.5 AND ABOUT 15 PARTS OF AN EMULSIFYING AGENT OF THE GROUPCONSISTING OF SULFONATED AND SULFATED ACIDS, ALCOHOLS AND ESTERSCONTAINING AN ALIPHATIC CHAIN OF BETWEEN 8 AND ABOUT 30 CARBON ATOMS,SULFONATED LIGNIN, CONDENSATION PRODUCTS OF POLYALKYLENE POLYAMINES WITHFATTY ACIDS CONTAINING BETWEEN 8 AND ABOUT 30 CARBON ATOMS, DIALKYLALKYLOL ALKYLAMIDE QUATERNARY AMMONIUM SALTS AND WATER-DISPERSIBLEREACTION PRODUCTS OF AN ALIPHATIC AMINE CONTAINING FROM 8 TO ABOUT 22CARBON ATOMS WITH EPICHLOROHYDRIN.